Title: CHM 434F/CHM 1206F SOLID STATE MATERIALS CHEMISTRY 2004
1CHM 434F/CHM 1206F SOLID STATE MATERIALS
CHEMISTRY 2004
- This course is designed as a follow-up to CHM
325, Polymer and Materials Chemistry, which
focused on structure-property-function relations
of selected classes of polymeric and inorganic
materials. - In this course we will be concerned with a
comprehensive investigation of a wide range of
synthetic methods for preparing diverse classes
of inorganic materials with properties that are
intentionally tailored for a particular use. - The lectures begin with a primer that covers key
aspects of the background of solid-state
materials, electronic band description of solids,
and connections between molecules and bonds in
materials chemistry and solids and bands in
solid-state physics.
2CHM 434F/CHM 1206F SOLID STATE MATERIALS
CHEMISTRY 2004
- This is followed by a survey of archetype solids
that have had a dramatic influence on the
materials world, new and exciting developments in
materials chemistry and a look into the crystal
ball at perceived future developments in
materials research, development and technology. - Strategies for synthesizing many different
classes of materials with intentionally designed
structures and compositions, textures and
morphologies, length scales and dimensionality
are then explored in detail emphasizing how to
control the relations between structure and
property of materials and ultimately function and
utility. - A number of contemporary issues in materials
research are critically evaluated to introduce
the student to recent highlights in the field of
materials chemistry - an emerging sub-discipline
of chemistry.
3CHM 434F/CHM 1206FSOLID STATE MATERIALS
CHEMISTRY 2004
- Solid-state materials synthesis methods
- Combinatorial materials chemistry robotic
synthesis - Contemporary issues in solid-state materials
chemistry case histories - Recommended text A. R. West, Solid State
Chemistry and its Applications, Wiley, 1997. - Reference texts D. W. Bruce, D. OHare,
Inorganic Materials, Second Edition, Wiley, 1997.
L. V. Interrante, M. J. Hampden-Smith, Chemistry
of Advanced Materials, Wiley-VCH, 1998. C. N. R.
Rao, J. Gopalakrishnan, New Directions in Solid
State Chemistry, Second Edition, Cambridge
University Press, 1997. L. Smart and E. Moore,
Solid State Chemistry, An Introduction, Chapman
and Hall, London, Second Edition. P. Ball, Made
to Measure, New Materials for the 21st Century,
Princeton University Press, 1997.
4COURSE EVALUATION 2004
- Mid-term test 90 min (25)
- Written term paper 3000 words (15)
- Written/oral assignments (10)
- Final examination 180 min (50)
5SCHEDULE FOR TERM WORK
- Assignment 1 14th October 2004 - short answer
paper - Assignment 2 28th October 2004, oral
presentation - mini-symposium, 6-9 pm - Last day to drop course 3rd November 2004
- Assignment 3 11th November 2004 - 90 minute
mid-term test - Assignment 4 25th November 2004 - term paper
- Assignment 5 Final exam TBA - December 2004
6PRIMER SOLID STATE MATERIALS CHEMISTRY
- Bonding in solids, ionic and covalent
- Most solids are not purely ionic or covalent,
polarization, dipolar, dispersion, Van der Waals
forces - Close packing concepts, hard spheres,
coordination number, substitutional-interstitial
sites - Primitive unit cell, standard crystal systems
(seven), lattices (fourteen Bravais),
translational and rotational symmetry (230 space
groups) - Factors controlling structure, stoichiometry,
stability (charge, size, space-filling concepts)
of solids - Basic concepts in bonding and electronic
properties of solids - Defects, doping, non-stoichiometry, effect on
properties - Electronic, optical, magnetic, charge-transport
behavior of solids
7BONDING AND ELECTRONIC PROPERTIES OF SOLIDS
CB
Eg
EF
EF
VB
W
Metal Semiconductor Insulator
Semimetal
Bloch-Wilson description of electron occupancy of
allowed energy bands for a classical metal,
semiconductor, insulator and semimetal.
8BONDING IN MATERIALS SIMPLE OR COMPLEX?
- IONIC COVALENT METALLIC VDW
- IONIC NaCl K3C60 K2Pt(CN)4Br0.3.2H2O
(RNH3)2MnCl4 - COVALENT Si (SN)x
C60 - METALLIC Cu
(TTF)2Br - VDW C6H6
- The bonding in these materials range from the
simplest ones on the diagonal of the matrix
(single type of bonding) to more complex of
diagonal (mixtures of bonding). Try to classify
each of these in terms of structure-bonding-proper
ties relations.
9PRIMER BLOCH-WILSON BAND DESCRIPTION OF SOLIDS
- Free electron traveling wave exp(ikx)
- Electron l, wave vector k 2p/l, p h/l
(h/2p)k quasi-momentum - Description of electrons in solids
- Modulated electron waves in a periodic crystal
potential U(x) - Bloch orbitals ?(x) exp(ikx)U(x)
- Electron wavelengths from ? to lattice spacing 2a
- Scattering of es by nuclei, standing waves at
Bragg condition nl 2a - Gives rise to forbidden energy band gap, Eg, and
VB and CB - First Brillouin zone runs from k ?p/a
- Band description in terms of density of states
(DOS), n(E) - Density of occupied and unoccupied states, n(E)
fFD(E)N(E) - Fermi Dirac distribution of electrons fFD(E)
1/(1 exp(EF-E)/kBT) - EF chemical potential of metal essentially
highest occupied level of VB - EF chemical potential of electrons, pinned for
intrinsic SCs 1/2(Ev Ec) - Electronic selection rules, optical transitions,
momentum k, electric dipole m - Direct transitions, Dk 0, kv kc, conservation
of momentum - Indirect transitions, Dk ? 0, kv kph kc,
conservation of momentum - Doping, H impurity model, n/p-doping, radius and
energies of electrons/holes - Effective mass of electrons/holes in solids,
me,h (h/2p)2/(d2E/dk2)
10PRIMER BLOCH-WILSON BAND DESCRIPTION OF SOLIDS
- Tight binding description of bands ?k
?1nexp(ikna)?n, periodic SALCAO Bloch orbitals - Essentially EHMO approximation for solids, Hii
coulomb, Hij resonance integrals, yields E(k) vs
k dispersion plots - Useful relations, orbital overlap, band width,
delocalization, band gap, band curvature, m,
mobility, conductivity - Junctions between SCs, Guasss theorem, contact
potential, band bending - Semiconductor np-junction diodes, M-SC junctions,
Schottky barriers/diodes, ohmic contacts - Photovoltaics, photodetectors
- Semiconductor-liquid junctions
- Solar cells and photoelectrochemical cells
- Semiconductor pnp and npn-junction bipolar
transistors, amplifiers, switches - Metal-oxide-semiconductor junction field effect
transistor, MOS-FET - Semiconductor LEDs, lasers, detectors
- Organic LEDs, FETs
- Quantum confined semiconductors, sheets, wires,
dots - Quantum superlattices
- Quantum devices, electronic/optical switches, MQW
lasers, SETs - Nanomaterials, nanoelectronics, nanophotonics,
nanomachines, nanofuture
11SOLID STATE MATERIALS CHEMISTRY MEETS CONDENSED
MATTER PHYSICSOVERCOMING THE JARGON BARRIER
- SOLID STATE BAND MOLECULAR ORBITAL
- Valence band, VB, continuous HOMO, discrete
- Conduction band, CB, continuous LUMO, discrete
- Fermi energy, EF (Electro)chemical potential
- Bloch orbital, delocalized Molecular orbital,
localized/delocalized - Tight binding band calculation EH molecular
orbital calculation - n-doping Reduction, pH scale base
- p-doping Oxidation, pH scale acid
- Band gap, Eg HOMO-LUMO gap
- Direct band gap Dipole allowed
- Indirect band gap Dipole forbidden
- Phonon, lattice vibration/libration Molecular
vibration/rotation - Peierls distortion, CDW Jahn Teller distortion
- Polarons, magnons, plasmons No analogues in
molecules
12ASSIGNMENT 1 Due 14th October 2004SOLIDS THAT
INFLUENCED THE MATERIALS WORLD AND WHY?Give a
brief 1-3 line descriptor for each material in
the list that illuminates the key features of
each material that were responsible for the
impact that it had on the high technology world
of advanced materialsThis assignment is
intended to get you reading around the subject of
solid state materials chemistryIt is very
demanding to provide succinct answers to each
part of this question, it will take much reading
and thinking
- ZrO2
- Na1xAl11O17x/2
- alpha-SiO2
- Si
- a-SiH
- alpha-AlPO4
- GaAs
- Na56Al56Si136O384
- (amine)xTaS2
- BaPb0.8Bi0.2O3
- SnFxO2-x
13- YBa2Cu3O7-x
- BaTiO3
- LiNbO3
- SrxLa1-xMnO3
- LixCoO2
- LaNi5
- Nb3Ge
- Ca10(PO4)6(OH)2
- TiS2
- ZnS
- WC
- (Si,Al)3(O,N)4
ASSIGNMENT 1 SOLIDS THAT INFLUENCED THE
MATERIALS WORLD AND WHY?
14- h-BN
- PbMo6Se8
- Y3Al5O12
- K2Pt(CN)4Br0.3
- (CH)n
- TTF(TCNQ)
- c-C, h-C
- C60
- K3C60
- SiOPc
- MgB2
- Porous Si
- nc-Si
- nc-TiO2
ASSIGNMENT 1 SOLIDS THAT INFLUENCED THE
MATERIALS WORLD AND WHY?
15- (SN)x
- HxWO3
- WO3-x
- CrxAl2-xO3
- AgBr
- Cu2HgI4
- gamma-AgI
- VO2
- CrO2
- AlxGa1-xPyAs1-y
- SmCo5
- Fe3O4
- PEO(LiClO4)
ASSIGNMENT 1, SOLIDS THAT INFLUENCED THE
MATERIALS WORLD AND WHY?
16ASSIGNMENT 2 CONTEMPORARY ISSUES IN MATERIALS
CHEMISTRY
- MINI-SYMPOSIUM 28th October 2004, 6-9 pm
- ORAL PRESENTATION
- MAXIMUM OF 3 TRANSPARENCIES
- MAXIMUM 5 MINUTES
- Note that these questions will require
considerable background reading and thought and
may not be able to be addressed until well into
the course - Also this type of oral presentation is amongst
the hardest to prepare and most demanding in
terms of successfully delivering the main message
17ASSIGNMENT 2 CONTEMPORARY ISSUES IN MATERIALS
CHEMISTRY, MINI-SYMPOSIUM
- 1. Why would the MoS2 faux fullerenes make ideal
solid lubricants? - 2. How would you use chemistry to make water flow
uphill? - 3. How would you synthesize hexagonal mesoporous
silica from a lyotropic liquid crystal? - 4. Why does nanocrystalline TiO2 enhance the RT
Li ionic conductivity of the polymer electrolyte
PEO-LiClO4 in a solid state Li intercalation
battery? - 5. How and why would you solublize a single wall
carbon nanotube? - 6. How and why would you functionalize a single
wall carbon nanotube? - 7. How can an electroluminescent thin film device
be made from monodispersed surfactant-capped CdSe
clusters? - 8. What are the advantages of using a single
walled carbon nanotube as the tip in an atomic
force microscope? - 9. How and why might you synthesize a concrete
spring? - 10. How would you synthesize a zeolite-like
material with a framework based upon either a
metal sulfide or metal-ligand complex rather than
an aluminosilicate?
18ASSIGNMENT 2 CONTEMPORARY ISSUES IN MATERIALS
CHEMISTRY, MINI-SYMPOSIUM
- 11. Why and how does the color and luminescence
of monodispersed surfactant-capped CdSe clusters
change with the size of the clusters? - 12. How would you make an abacus from C60?
- 13. How would you use a thermotropic liquid
crystal and a polymer to electrically control the - transmission of light through a glass
window? - 14. How would you use a thermotropic liquid
crystal to tune the optical Bragg reflection from
a silica colloidal photonic crystal - 15. How and why does the magnetotactic bacteria
synthesize a chain of ferromagnetic clusters? - 16. How could you build a chemical sensor from
monodispersed latex spheres? - 17. How does the intermetallic LaNi5Hx function
as a cathode in an alkaline-nickel hydroxide - battery?
- 18. How would you use a combinatorial materials
chemistry approach to find a better lithium solid
state battery cathode or anode?
19ASSIGNMENT 2 CONTEMPORARY ISSUES IN MATERIALS
CHEMISTRY, MINI-SYMPOSIUM
- 19. How can information be stored in CoCuCo metal
magnetic multilayers? - 20. How would you synthesize a plastic light
emitting diode? - 21. How and why would you synthesize a colloidal
crystal with a diamond lattice of silica
microspheres - 22. Why is a membrane made out of Nafion, a
perfluorosulphonic acid, the solid - electrolyte-separator of choice in a
hydrogen-oxygen fuel cell? Could you find a new
material to make a better membrane than Nafion? - 23. Why does the Tc of BiSrCuO type ceramic
superconductors not change on intercalating a 5
nm thickness (cetylpyridinium)2HgI4 bilayer
between the BiO layer-planes? - 24. How can a single electron transistor (SET) be
made from a single 5 nm diameter CdSe cluster? - 25. How can a transistor be made from just one
single walled carbon nanotube? - 26. Why does the jewelers chisel preferentially
cleave diamond along 111? - 27. Why does single crystal Si display chemical
anisotropic etching in alkaline solutions that is
faster along 111 than 100? How is this
attribute used to make microelectro-mechanical
machines MEMS?
20ASSIGNMENT 2 CONTEMPORARY ISSUES IN MATERIALS
CHEMISTRY, MINI-SYMPOSIUM
- 28. Why does an ensemble of monodisperse 5 nm CdS
nanoclusters, excited with UV light, display
continuous bright green-blue luminescence,
whereas a single nanocluster shows flashing
green? - 29. Why does nitric acid preferentially open the
end of a closed carbon nanotube? - 30. Why are Fe, Co, Ni the only ferromagnetic
transition metals? - 31. Why does dye-sensitized nanocrystalline
nc-TiO2 greatly enhance the light-to-electricity
conversion efficiency of a photo-regenerative
solar cell with the following construction
ITOnc-TiO2, Ru(bipy)32I-, I2, CH3CNPt? - 32. Why is the fracture toughness of the calcite
nacre shell of the mollusk 1000x that of calcite
itself? - 33. How many ways can you think of tuning the
wavelength of an optical Bragg reflector built of
a face centered cubic colloidal crystal array of
silica spheres? Why would you want to do this? -
21ASSIGNMENT 2 CONTEMPORARY ISSUES IN MATERIALS
CHEMISTRY, MINI-SYMPOSIUM
- 34. How does the anodic oxidation of a wafer of
p-Si in aqueous HF, lead to self-limiting
monodispersed pore formation and a novel material
that is photo- and electroluminescent? With this
knowledge how would you build an array of
wavelength tunable, individually addressable
LEDs on a Si wafer based on this chemistry, that
could be used for an active matrix flat panel
display? - 35. How would you make an alumina or silicon thin
disc with a hcp array of parallel nanoscale
channels starting with an aluminum disc or
silicon wafer and then use it to make free
standing nanorod replicas comprised of Ag and Au
bar coded nanoscale segments - 36. How would you synthesize Ca2C60? Assuming a
fcc arrangement of C60 molecules and Ca residing
in octahedral interstices, explain why the
material is semiconducting? - 37. Given just a glass slide, curved lens,
polarizers and cholesteryl esters, how would you
make a clinical thermometer with a precision of
0.1oC? - 38. Which organic, inorganic and polymeric
materials are in the global battle for control of
the electroluminescent, electrochromic,
electrophoretic and liquid crystal flat panel
display market, and what properties of the
material will make it a winner?
22ASSIGNMENT 2 CONTEMPORARY ISSUES IN MATERIALS
CHEMISTRY, MINI-SYMPOSIUM
- 39. How would you mimic biomineralization of
magnetotactic bacteria in the laboratory to
synthesize better data storage materials? - 40. How might you make a buckyball switch?
- 41. Given Pt, how would you devise a resistless
lithography for Si wafers? - 42. How would you synthesize and self-assemble
semiconductor nanowires into nanoscale devices
like, lasers, LEDs, diodes, transistors, logic
circuits? Can you use this knowledge to
synthesize a better computer than current state
of the art ones? - 43. How could you self-assemble micron diameter
silica spheres into a micron scale checker board
pattern? - 44. How might you write the Lords prayer on the
head of a gold pin? - 45. Devise a way of synthesizing a micron scale
checker board pattern of vertically aligned
carbon nanotubes or zinc oxide nanowires? - 46. How could you store large amounts of
information in a fcc colloidal crystal array of
microspheres? - 47. How could you build a chemical sensor from
monodispersed polymer spheres? - 48. Materials options for the safe storage of
hydrogen for fuel cell powered cars - 49. Devise a way to synthesize a AuAg nanocluster
inside a hollow AuAg nanosphere
23ASSIGNMENT 3 INDEPENDENT WRITTEN PROJECT
SUGGESTED TOPICS
- Focus your attention on materials design,
synthesis, characterization, structure, property
and function relations and the relevance of the
materials to advanced technologies - High marks for this assignment will require more
than just a written representation of what you
find in books, reviews and papers - it will also
require some evidence of creative ideas, original
thinking and critical commentary - A typed version is required of not more than 3000
words, not including figures and tables. -
- Hand in a bound copy to Professor Geoffrey A.
Ozin before 25th November 2004
24ASSIGNMENT 3 INDEPENDENT WRITTEN PROJECT
SUGGESTED TOPICS
- 1. Evoking light emission from silicon - LEDs and
lasers made of silicon - science fiction or
reality? - 2. Endohedral and exohedral fullerenes - what are
they good for? - 3. Inorganic polymers - materials for the next
century? - 4. Non-oxide open-framework materials - past,
present and do they have a future? - 5. Materials harder than diamond - can they be
made and why do we need them? - 6. Supramolecular templating of mesostructured
inorganics - a solution looking for a problem? - 7. Plastic electronics for the next millenium-
goodbye silicon? - 8. Carbon nanotubes - better than
Buckminsterfullerene C60? - 9. Capped semiconductor nanoclusters and
nanocluster superlattices - what are they good
for? - 10. Capped gold nanoclusters and gold nanocluster
superlattices - would Faraday be impressed? - 11. Electrides - chemistry with the electron - do
they have a future? - 12. Magic of magnetic multilayers - giant
magnetoresistance data storage materials - can
they compete? - 13. Molecular magnetism - a basis for new
materials? - 14. Photorefractive materials for manipulating
light - do they have a bright future?. - 15. Nanoscale patterning and imaging with
scanning probe microscopes - smaller, faster,
better things? - 16. High Tc superconductors - will they ever
reach RT and be useful? - 17. Kinetics of intercalation - getting between
the sheets as fast as possible - why do we need
to do this? - 18. Layer-by-layer assembly of inorganic thin
films - why do we need such designer multilayers?
25ASSIGNMENT 3 INDEPENDENT WRITTEN PROJECT
SUGGESTED TOPICS
- 19. Alkane thiol self-assembled monolayers (SAMs)
- what are they good for? - 20. Biomimetic inorganic materials chemistry -
why steal Natures best ideas? - 21. Why grow inorganic crystals in space?
- 22. Information storage materials - how dense can
you get? - 23. Microelectrochemical transistors and diodes -
materials chemistry on a chip that did not make
it, why?. - 24. Photonic band gap materials for a photonics
revolution - trapping light - a new religion?. - 25. Dye sensitized nanocrystalline semiconductors
- towards high efficiency solar cells? - 26. Fuel cell materials - future of the electric
vehicle - science fiction or reality? - 27. Smart window materials - energy conservation
and privacy - how do they work? - 28. Forbidden symmetry - quasi-crystals for
quasi-technologies? - 29. Nanocrystalline materials - will they really
impact science and technology? - 31. Silica film must be at least 4-5 atoms thick
to be an insulator - end of the road for silicon
electronics? - 32. MEMS - microelectromechanical machines - can
they really do big things? - 33. Nanowire nanocomputer - science fiction or
reality? - 34. On-chip lithium solid state microbatteries -
towards on board power? - 35. Why has the subject of nanosafety recently
become a hot button scientific and political
issue? - 36. Materials self-assembly over all scales -
panoscopic view of materials? - 37. Electrophoresis, electrochromicity,
electrodewettability materials battle for
electronic ink?
26ASSIGNMENT 3 INDEPENDENT WRITTEN PROJECT
SUGGESTED TOPICS
- 38. Slow photons in photonic crystals, what are
they good for? - 39. Barcoded nanorods - do they have a future in
bionanotechnology? - 40. Dynamic self-assembly - towards complex
systems in chemistry, physics and biology? - 41. Periodic mesoporous organosilica materials -
could they make it as a new generation of low
dielectric constant materials for microelectronic
packaging. - 42. Molecular electronics - a problem without a
solution? - 43. Materials for a spintronic revolution - can
we really compute with electron spin rather than
charge? - 44. How would you prove Richard Feynmann right
and write all the information in the library of
congress on the head of a pin using a chemical
approach?